Triarylmethane dyestuff



Patented Au 8, 1933 isnsn TREE LME'EE;

Muller, Cologne-o- Leverlrusen-l.

Leverhusen-i/Viesdorf,

fear Wahl, Leyeruusen G W'erlt, Werner -e,' 'Kohn, Teunei, Germany, assignors to General Anilinevlorks, lna, New York, N. 37L,

a Corporation of Delaware No Drawing. Applicationhugust 5, i932, Serial No. EZ'ZJWS, and in Germany September 12,

' 7 Claims,

may be represented by the probable general iormula:

, Ho-cz EAr (hI-a1kSOsl l)n r 3 V wherein Ar stands for a radical of the benzene or naphthalene series, forinstance, for a benzene or naphthalene nucleus which may be su'csti tuted by alkyl, such as methyl and ethyl, alkoxy, such as methoxy andethoxy, halogen,- the amino group, a substituted amino group, as a diallzyl amino group or a sulfonic acid group, it stands. for hydrogen, alkyl, aryl or-aralkyl, for instance for methyl, ethyLpropyl, outyl or hen'syl and phenyl, whereinthe nuclei may he suhstitutedffor instance, by halogen, methyl, ethyl, methoxy, ethcxy or a sulfonic acid group, all stands for' an alkylene group, such as a methyl- I one, ethylene, propylene or butylene roup, and

containing at least one aromatic amino group.

able aldehyde to'f the corresponding leucotriarylmethane compound and oxidising the same to form the dyestuff.

Another method or" preparing our dyestuffs resides in causing a halogenallzylsultonic acid to act upon a dyestufi of the triarylmethane series Finally the new dyestufis are obtainable l actingwith an alkali rnetai 'sulfite at an elevated temperature upon a triaryhnethane dyestuff containing at least once the a, group same as statedacove. In this manner it possilole to synthesize triarylmethane dyestuffs cona stated above, condensing the same with a suittaining besides the aminoallaylsulfonic acid group or groups also aininohydroxyalkyl groups. This can he achieved by starting with such triarylmethane compounds of the kind referred to in v "ch the aminohydroxyalkyl groups are only tally esteriiied or, by reacting upon the 'triarylniethane dyestuffs in which all aminohydroxyalkyl groupsare esterified-with a quantity of an alkali metal sulfite insuficient for trans ing the esteriiied aininohydroxyalkyl groups to aniinosulialityl greens.v

-stead of producing the group lh-R-alle- SOsli group characteristic for our new dyestuffs in triarylmethane dyestuits containing least one aroma 0 amino group or an esterified lzyl group, or synthesizing the such coinnounds containing al-' i stic group, there may he started with a d arylinethane compound. in which before or after-the synthesis of thet"'arylinethane dyestuil according 'to 7 known irethods there is produced our characteristic group I I All the methods of preparing our new dyestuffs areequi'valent to each othe',

If there are used theleuco compounds of the triarylmethane dyestuffs as starting materials, or if in the process of manufacture our new dyestuils are obtained in the leuco form, for instance, hy'the cticn of alkali metal suifite, they can be transformed into the dyestuifs by oxidation in the known manner.

Our dyestuffs are generally water soluble, dark, metallic lustrous powders, dyeing animal such as wool orsiilz, generally reddishviolet to blue to green shades. Compared with riaryhnethane dyestuffs or" similar constitution, for example, with those containing instead of the a sulrohenzyl radical, they generally are distinguished by an increased solubility in water and an improved clearness oi the shades obtained therewith. v

The invention is illustrated by the following examples, withoutheing limited thereto:

aminohydroxy Example 1.-l moi. of p -diethylaininoben zaldehyde is heated with 2 1101s. of o-tolyltaurine in a weakly sulfu ic acid solution, untilthe condensation is complete. The leuco compound is oxidized either after previously isolating by salting out with sodium sulfate or directly in the condensation solution, for example by adding to the solution of the leuco acid prepared from 18 grams of p-diethylarninobenzaldehyde, 18 g. of sulfuric acid, 1 g. or acetic acid and 16 g. of lead peroxide, while stirring.

The reddish violet dyestuif formed having in its carbinol form the following formula:

| I 1 HOgS-CHrCHz-N-QEIQ N-OHz-OHz-S 0311 I H CH3 0113 The same dyestuff is obtainable by condensing 1 molecular proportion of p-diethylaminobenzaldehyde with 2 molecular proportions of phenylethyltaurine in weakly acid solution, and oxidizing the leuco compound formed, for example, with 1 molecular proportion of lead peroxide and hydrochloric acid.

Example 3.-Tetramethyldiaminodiphenylmethanehydrol and m-tolylethyltaurine in molecular proportions are heated in aqueous weakly acid solution, until the hydrol has disappeared. The leuco compound formed is oxidized with 1 molecular proportion of lead peroxide in hydrochloric acid solution to form a bluish-violet dyestuif which can be dyed according to the method known for dyeing alkali violet. In its carbinol form the dyeing .has the following formula:

CH3 N Example 4.--1 molecular proportion of tetraethyl-4.4-diamino-3"-a1ninotriphenylmethane is heated at 100 0., one molecular proportion of the sodium salt of chloroethanesulfonic acid, and the mass is stirred until solidification has taken place. The leuco formed is oxidized according to known methods to a bluish-green triarylmethane dyestuff. In its carbinol form the dyestuif has the following formula:

H5Cz Example 5.--3 molecular proportions of butylphenyltaurine are heated with 1 molecular proportion of formaldehyde in aqueous weakly acid solution, until the formaldehyde has disappeared. By the addition of 2 molecular proportions of chromic acid is oxidized to form a dyestuff having in the carbinol form the probable formula:

It dyes the animal fiber, for example wool, very clear bluish-violet shades.

Example 6.-1 molecular proportion of p-sulfobenzaldehyde is condensed with 2 molecular proportions of butyl-m-tolyltaurine; the leuco compound formed is oxidized to a green dyestuff. 1 part of this dyestuff is heated with 2 parts of p-phenetidine at 100 C. until the green color has turned to blue (several hours). The melt is poured into water, and the dyestuff is precipitated by the addition of hydrochloric acid. In form of its alkali metal salt it is easily soluble in water and dyes Wool and silk greenish-blue shades. In the carbinol form it has the following formula:

CH3 G N (inform-sonar g E When performing the second condensation with aniline instead of p-phenetidine a dyestuff dyeing redder is obtained, while, when using o-toluidine instead of p-phenetidine, there is obtained a dyestuff yielding still more redder shades.

Example 7.2 molecular proportions of benzylm-tolyltaurine and 1 molecular proportion of o-chlorobenzaldehyde are heated in aqueous suspension until the benzyl-m-tolyltaurine has disappeared. The leuco dyestuff is oxodized with lead peroxide and hydrochloric acid to form the dyestuff which dyes wool clear green shades. In the carbinol form it has the following formula:

Example 8.-1 molecular proportion of p diethylamino-benzaldehyde is condensed in weakly acid solution with '2 molecular proportions of l benzylphenyltaurine.

formed is oxidized with potassium bichromate following formula:

Example 9.63 parts by weight of an aqueous paste of Michlers hydrol, corresponding to 27 parts by weight of hydrol, are dissolved in 100 parts by weight of a 10% aqueous sulfuric acid. Thereto is added a suspension of 33 parts by weight of diphenyltaurine in 25 parts by weight of 2. 20%, aqueous sulfuric acid and 26 parts of hot water. Condensation to form the leuco compound is performed on the boiling water bath. The reaction mass is diluted with water and oxidized in the usual manner to form the dyestuff. After isolation and purification it is obtainedas a lue powder, dyeing the'animal fiber from a mineral acid bath reddish-blue shades. In the formula:

, on Example 10.--67 partsby weight ofvthe sodium :salt of the sulfuric acid ester of di-(2 ohloroi- N =CH2 obtainable for example by introducing the corresponding methane compound into sulfuric acid scribed in Example 10.

the bulk of the sodium salt of the di-(Z-chlorol- [sulfoethylbutylamino] phenyl) 1-methane separates in form .of small colorless crystals. 7 The separation can be completed by the addition of aqueous saturated common salt solution. The diphenylmethane compound thus obtained is then oxidized to form the corresponding hydrol and is condensed with di thylaniline in the usual 7 manner. The dyestuff thus obtained has in the carbinol form the following formula:

A I I OiHs I I C2115 HOiS-HiOz OH Gilli-S0311 Example 11.-The aqueous paste of the sodium salt of the sulfuric acid ester-prepared from 50 parts byweight of the leuco base of the constitution: 7 v

. HOCzHi is heated in a closed vessel at a temperature of 150 C; withi50 parts by weight of sodium sulfite for etc 5 hours. The mass is worked up as de- Thus' is obtained the sodium salt of the leuco acid of the following formula:

in form of water soluble colorless crystals. Also the free acid is soluble in water and acids. By oxidation according to the usual methods, for example in acid solution with lead peroxide, a blue dyestuff is obtained, dyeing the animal fiber clear greenish-blue shades.

When acting upon the sulfuric acid ester described in paragraph 1 with less sodium sulfite, for example, about parts by weight, there is obtained aleuco acid still exerting strongly basic properties. In this case probably only one ester group has been transformed into the sulfonic acid" group, while the other sulfonic acid groupshave been saponified. The blue dyestufi obtained therefrom by oxidation has only weakly acid properties.

furic acid ester of 60 parts by weight of a leuco base obtainable by condensation of 1 mol. of

o-chlorobenzaldehyde with 2 mols. of N -hydr0xypropylbutylaniline, is heated with 120 parts by weight of crystallized sodium sulfite for 6 hours to a temperature of 1309 3. The reaction mass is worked upas described in Example 19.

In this manner there is obtained the sodium Example 1 2.The moist sodium salt of the sul- 1 1 soul 2 Example 13.'72 parts by weight of the sulfuric acid ester (sodium salt) of the dyestuif having the probable formula:

are heated in a closed vessel with 150 parts by weight of crystallized sodium sulfite for 8 hours at a temperature of 140 C. The weakly violet colored reaction mass is poured into water and rendered acid. After blowing'air through the solution, until the sulfuric acid has disappeared, the dyestuff reduced in the reaction is oxidized in the usual manner. By salting out there is obtained the di -(l l sulfoethylbutylamino) triphenylmethane dyestuif in form of a reddish bronce resine, dyeing the animal fiber clear green shades. It is easily: soluble in water and has in the carbinol form the following formula:

Example 14.60 parts by weight of the dyestuff of the probable formula:

GzHrOSOsNKL are heated with 100 parts by weight of water and 150 parts by weight of crystallized sodium sulfite for 4 to 5 hours at a temperature of l20130 C. The reaction mass is worked up as described in Example 10. There is obtained a bluish-violet dyestuff which in its properties is identical to that obtainable according to Example 5.

Example 15.51 parts of butylphenylaminopropane-sulfonic acid of the probable constitution:

are condensed in the usual manner to the leucocompound with 200 parts of water and 15 parts of o-chlorobenzaldehyde. By neutralizing with alkali and salting out of the alkaline solution there is obtained the crystallized sodium salt, and, when oxidizing in the usual manner to the dyestufi there yields an easily soluble dyestuff,

dyeing the animal fiber clear green shades. In

its carbinol form it has the probable formula:

Example 16.1 molecular proportion of Michlers hydrol is heated for about 1 hour in aqueous weakly sulfuric acid solution with 1 molecular proportion with a-naphthyltaurine. The leuco compound formed is separated by neutralizing and is oxidized with lead peroxide and hydrochloric acid. The dyestulf having in the carbinol form probably the following formula:

I NH

(1H2'CH2SO3H dyes wool or tanned cotton blue shades.

Example 17.-The dyestuif obtained by condensing 1 molecular proportion of o-sulfobenzaldehyde and 2 molecular proportions of butylphenyltaurine in acid solution, followed by oxidation, having in the carbinol form the following formula:

v orn-om-s 03H CJHEI 110-0 N \CH2CH2-S 03H l soin dyes wool and silk clear greenish-blue shades fast to alkalies.

Example 18.--The dyestuff obtained by condensing two molecular proportions of butylphenyltaurine with 1 molecular proportion of formaldehyde in weakly acid solution and oxidizing the cliphenylmethane compound formed with sulfuric acid and potassium bichromate in CHz-CHz-S 03H 0 H5 dyes wool and silk clear violet shades.

Example 19. The dyestuff obtained byoon densingl molecular proportion of p-e'hloro benzalclehyde' 'an dj2' molecular proportions of butylphenyltaurinefollowed by oxidation, is

5 heated with thesarnee uantity of p-phenetidine at 100 C. for 31191118. excess pheneti ine is dissolved by the addition of dilute hydrochloric acid and the dyestufi having in the earbinol form the formula:

is isolated from its solution in the usual ,It. is in form of its alkali metal salts easily soluble in water, dyeing Wool and silk brilliant r ddish-blue shades.

A dyestuff dyeing somewhat redder is obtained by substituting the p-phenetidine by aniline, by

3 substituting the p-phenetidine by o-toluidine, a

I butyl-m-tolyltaurinein weakly acid so dyestuff dyeing still more red is obtained.

Example Zi -The 'dyestufi obtained densing 1 molecular proportion of p-ui noloenzaldehydewith 2 molecular prop oxidizing the leuco compound forin ample. with 1 molecular proportion Oi lead oxide and hydrochloric acid. 1n the car form the dyestuf? has the followin formula:

WhereinAr stands for a radical of the benzene or naphthalene series, B stands for hydrogen,

,alkyl, aryl or aralkyl, alk stands for an allzylene V "gr0up and nfstands for one of the numbers green shades.

one to three, being in term of their alkali metal salts dark metallic lustrous powders, dyeing animal fibers generally reddish-violet to blue to 2. Triarylmethane dyestufis having in the carbinol formthe probable general formula:

dyeing W001, and sill: clear violet shades.

W1181ei11.[ii stands for a radicalof the benzene series, stands for hydrogen, alkyl, aryl or arallryl, allr stands for an alkylene group, and H 77 t a Y I. J. V

it stands ior one or the nurnbers one to three,

beinginiorni of vtheir alkali metal salts dark 80 o. Triarylneo ane dyestnfis havin in the carbinol form the probable general formula:

soln-onz o iii-N" I Y B jut-eel by alkyl, Ar stands for a radical of the benzene seri s and R stands for benzyl or an allryl group, losing in form of their alkali metal salts dart: metallic lustrous powders, dyeing anigenerally reddish-violet to blue to ne dyestuffs having in the cariooable general formula:

soin or-n oriz inr where n the nzene nuclei Ar and Ar may be substituted in methyl, the benzene'nucleus Ar may he by substitnents selected from the group consisting of dialleylaniino, phenyl so, allroxy, halogen and the svlfonic acid gzi'onp, stands for benzylor an allryl group, being iniorn of their alkali nietalsalts dark metallic lu. rons powders, dyeing anirnal fibers generally reddishwiolet to blue to green shades.

5,. The triarylrnethane dyestuff having in the carbinol form the following formula:

dyeing wool and sill; violet snades.

fifThe triarylnlethane dyestufif having in the carhinol form the following formula: O4Hlom-om -soni CzHs '7. The triarylmethane dyestufi having in the dyeing wool and silk very clear greenish-blue I carbinol form the following formula:

shades.

OTTMAR WAHL.

WERNER MI'JLLER. ADOLF KOHN. ERNST TEUPEL. 

